Plasticized vinyl halide resins and electrical conductors insulated therewith



Nov. 11, 1952 R. K. GRIFFITH INYL AL 2,617,779 HALIDE RES AND ELECTRICAL CTORS INSUL D THEREWITH Filed May 1949 ASTICIZED V CONDU Inventors Roland K. 'Ffi Henry C. soh,Jn,

Their Arbor-neg.

Patented Nov. 11, 1952 izmsrr clznn VINNYL HALmnnEsINs AN ELECTRICAL CONDUCT-OBS INSULATED THEB W H Roland 1K. Griffith, Schenectady, an

Nelson, 1n; Averill Park, Y,, W -;Qener l Electric Company, a my o 'ra W H a nea ly to. to

fi ii cq ly gzg, 1949, Serial No. 96,132

:This invention relates- :to --plasti cized vinyl resins. tMore pamtioulari ly', tlfie-presentinvention is concerned with vinyl :halide resins plasticized with a composition of matter comprising the liquid product ofreactiOn-of a mixture of ingredients comp ising l) a; lsatureted', aliphatic dihiydric alcohol conta 'ing "atlea'st three-carbon atoms, (2) a; -satura td, liphatic dicdrboxylic acid, I and (3 i a saturated, eiliphatic ino'nohydric alcohol, the said monohjrdric aloohol acting as an esterifyingchain-stopperateach end of the linear "ester chain for1ned hy tliej reaction between th'eforesaid dihydric alcohol end dicerboxylic acid. "The various plasticizersand methods for preparing' th'e same-employed -in the practice of the instant invention arefmoi e particularly disclosed and claiined in our copend-ing application -seifitilNo-c 96,1 j miw" abendoned, filed concurrently herewith nvzagsisiggned to -the' some assignee as the "present invention; which epiph: cation; for"purposes -off'"brevity, made 4 part ofitheinstant pp1i at1qn asttc all its' disclosures.

'Ma-ny plasticizers"harvebeeri feniployediorplasticiz'in'g vinyl halide resii'is. In aln'iost everyoase it has b'e'ennece ss" I if it" is desired to "obtain a -iiarti'cula'r property in-the plasticized mate al. ""Th-us w hereafs'one plasticizer miht imp 'v the-"10w; temperature flexibility ofthevi-ny ailide resin, suc plasticizermightwell betoo olatile}elt elevetegftefipera ture's =wheh inc61 pordtecinthe vinylffhalide resin. ;Mor'eover,-whereels' 'soineplasticiz'ers nfigfit have-goodlight an weatherije'sis'tance,"-the ;s5n e plasticizer niight be idefici'ent in either 1 its oil resistance or itsfcornpeti bility' with the vinyl halide resi-nI 'We haVe now: discovered-that-ai certain class of chain-stopped linear; Lperznanenflywfusibh liquid polyesters, more/particularly described above; have :eminentisuitabilityas plasticizersafor vinyl haIi-deare'sins and thesea'linea'r lchainrstopped polyesters"?incorporate-many of =the more desir- -ab1e-properties foundi individually ineothenplasticizers. Unexpectedly, wexhave discdveredthat porated; in al.vinylvhalidepresinrby1suitablemeans imparts to such';- re sin outstanding ii'lexibilitx,

good 10w;temperaturefl xibility;lightrresistan n Weathe -.es stan e.- aserwell has .outstandin o l 1res stt,v e. ;.a. L-in addit on. vtheuplost cized y meter-choc is' 45, this particular 1 classtoiyplasticizers' awhen :.-inco1t'- resin. The use of such plasticizers is unexgectil m hs w m th -tac rt h s n es i i mi g: .i f

Q 'tion btw en i mixture or g 1) urned-( liphatic h i elcpho 0 n '9 s fir a bb d fil pliatic di'carbb'xylic n aii ts i compatibilityw thiyinyl 711541 e resins and lower volatimy, v o

.l m epering the claim u o psipion's m wherehmequalsr from-1 t0'10, preferably from 2 toatiifor instancesmalonicl siicciniE aairiicf glu: tar c, -pimelioi'z sehacicg.iazlai} suberic, etc." alcids. -;B ranch ed; chaimisomer's iofvlsuch acids inely also be ernplpyed. :We preferL to use"dicaalo'oiifi "b alcids containing from 4 to 1-0 ito'tal crbdnatoins inlufilif :thecan yemups 7 I t s ppssibletoikdesignthe individual plasticiger molecule so ;as to irive'; at" compositions T I 3 which are chain-stopped and which conform to certain predetermined molecular chain lengths. Such compositions of matter may be considered as corresponding to the general formula is an integer equal to from 1 to 10, preferably,

from 3 to 7. The simplest composition. obtain able may be represented by the formula o o I ZO(H3R(]O o -E-n-iL-o-z 4 411,0 where R, R and Z havev the meanings given above,

From the foregoing formu a it will be apparent thatthe length of .the linear chain-stopped, liquid, permanently fusible polyester employed as a plasticizer'can be increased or decreased so as to influence the properties of the final'composition. By being able to tailor the molecule and by controlling the proportion and type of ingredients,

it is also possible to control the viscosity of the final plasticizer composition,

In preparing the plasticizers, the reactants are preferably charged to a reaction vessel equipped with stirring and heating means. Small amounts of the usual acidic catalysts ordinarily employed in esterification processes as, for instance, hydrochloric acid and sulfuricacid, may also be added to the reaction mixture to expeditethe formation of the claimed compositions of matter, although We have found in' many instances'this is not essential. J Thereafter,'. the mixture is heated at elevated temperatures, for example, from about 125 to 250 C.,for a period of from 2 to l hours or more while at the same time removing the water of esterification formedduring the 'process. The heating is preferably conducted in a manner calculated to cause an incremental increase in the temperatures of thereaction mass during the period of the reaction with a concurrent decrease in the acid number. If desired, the reaction may be conducted in the presence of selected solvents which are inert to the reactants or the reaction product. I I

Generally-the proportions of ingredients may be varied within'wide limits depending upon the size of the molecule desired. Thus, on a molar basis, we may use for each mol of the dihydric alcohol at least two mols of the dicarboxylic acid and two mols of the monohydric alcohol suificient to effect chain stopping of the linear polyester.

Inpreparing theplasticizers, if suitable molar equivalents of the ingredients are present in the reaction mixture, continued heating at elevated temperatures will cause the acid value of the final reaction product to be lower. In many applications, especially in general plasticizing applications, higher acid values can be tolerated satisfactorily, However, where it is importantto maintain optimum electrical properties, it has been found eminently- .desirable and in many cases necessary to bring the acid value of the final reaction product to below 5 as pointed out previously, e, g., from 0.2 to 4.

As pointed out previously, the plasticizer can be tailored to any desired'molecular weight or linearity dependingon the molar proportions and the ingredients used in the reaction mixture. For most applications, on a molar ratio basis, we have found it preferable to use from 4 to 8 mols of the dicarboxylic acid in the reaction mixture. The amount of the dihydric alcohol employed in such instances is generally .equal to n-l-i-a: mols where n is equal to the number of mols of the dicarboxylic acid and a: is equal to at least a slight molar excess or even a large molar excess, for example, from 0.1 to 2 or more molar excess of the dihydric alcohol necessary to cause the reaction to go to completion.

The chain-stopping monohydric alcohol is preferably present in a proportion of at least 2 mols, excess amounts remaining unreacted and requiring later removal in isolation and purificationof the chain-stopped reaction product.

However, an excess of the monohydric alcohol doesassist in causing the reaction to go to completion by acting as an entraining agent for thewater of esterification, However, extreme care shouldpbe exercised-to remove all traces of the excess monohydric, saturatedaliphatic alco- Generally, it is desired: formost plasticizing applications where good compatibility, working and handling characteristics,and low volatility are essential propertiesyto maintain the viscosity within the range ofabout 250-4000 centipoises at 25 C., e.-g from 350-to 250 0 centipoises. In all casesthe actual viscosity will depend upon the molar ratio of the dicarboxylic acid to the dihydric alcohol, the ingredients used, the degree of condensation betweenthese two reactants as evidenced, by the lowering of the acid value, etc. i v

The vinyl halide resins for, which the chainstopped' linear polyesters disclosed and claimed in our aforementioned application, Serial No. 96,131, are eminently suitable as plasticizers, comprise the product of polymerization of a mass containing a vinyl halide, for instance, a predominant proportion of the vinyl halide. Among such compositionsare (1);,the polyvinyl halides, such as, for example, polyvinyl,;chloride (including the different molecular weight forms, ,e. g., gammapolyvinyl chloride, etc.-), polyvinyl bromide, etc. (2) vinylresins producedbythe conjoint polymerization of a vinyl halide, e. 'g., vinyl chloride, and avinyl ester of a lower saturatedaliphatic monocarboxylic acid, for, instance, vinyl acetate (such vinyl chloride-vinyl acetatejcopolymers being available under the trade name of Vinylite resins wherein the vinyl chloride component is present in a preponderant amount), vinyl propionate, vinyl butyrate, vinyl hexoate, vinyl acetobutyrate, vinyl chloroacetate, vinyl chloropropionate, etc.,,it being understood from the foregoing examples that the ,term .lower' saturated aliphatic monocarboxylicacid embraces ones containing at most six carbonatoms; .(3) vinyl resins produced by the conjoint'p'olymerization of a vinyl halide and an acrylic compound, e. g.; the copolymers of .vinyl chloride with, for example, ethyl methacrylate,.methyl methacrylate, benzyl'or chlorobenzyl acrylate, methyl chloroacrylate, .etc.; (4) copolymersof a vinyl halide, e. g;, vinyl chloride, and a vinylidene halide, e. g., vinylidene chloride; and (5) many other vinyl resin copolymers, such as the copolymers of three-component systems, "for example, vinyl chloride, vinyl acetate and ethyl methacrylate, etc. As will be understood by those skilled in the art, other multi-component copolymers may be used, the only requirement being that at least enigm formed as a result of reacting a mixture of ingredients comprising (1) 1 a saturatedaliphatic dihydric alcohol containing at least three carbon atoms, (2) a saturated aliphatic dicarboxylic acid and (3) a saturated aliphatic monohydr'icalcohol are more particularly disclosed and claimedin our aforementioned application, which by reference is made apart of *this application. For many applications we prefe'r'to use as plasticizers for the aforementioned vinyl halide resinscompositions resulting from the reaction of a mixture of ingredients comprising (1) a saturated aliphatic dihydric alcohol containing from three to eight carbon atoms, (2) a saturated aliphatic dicarboxylic acid containing from four to ten carbon atoms, and (3) a monohydricsaturated aliphatic alcohol containing from six to twelve carbon atoms. The longer chain branched and normal monohydric alcohols tend to improve the compatibility of the plasticizer with the vinyl halide resin. By a proper choice of reactants in making the plasticizer, it is possible to tailor a particular plasticizer for a certain application, taking into account the ultimate use to which the plasticized vinyl halide resin is intended to be put.

In order that those skilled in the-art may better understand how the present invention may be practiced, the following example is given by way of illustration and not by way of limitation. All parts are by weight.

EXAMPLE" 1 Parts Molar Ratio Adipic acid I023. 7. Propylene glycol 502. 2 6.6. Iso-octyl alcohol I 273. 4 2. l

Mixture of branched chain isomers of octyl alcohol.

The above mixture was heated under a nitrogenatmosphere to a temperature; of from 150 to 155 C. for about 2 hours until an acid value of 200 was obtained, then to 180-185? C. for 2 additional hours until an aeic'lvalue of 100, was obtained, thereafter 3 'more hours at 230-235 C. until anacid value of 25 was obtained, and thereafterraised to 250C. for 4 hours 'untilan acid value of 1.34 was obtained. During the reaction the water of =esterification was removed fromthe. reacting mass. Any remaining, unreacted ingredients were removed from the reaction mass by passing a stream of nitrogen through the mass to leave a liquid, permanentlyfusible, chain-stopped "product having a "viscosity o f"l -45O "centipoises. I j

The above liquid plasticizer was mixed with the-following ingredients in the stated propoi tions: I

Ingredients: I r I Parts Copolymer of vinyl chloride and,

15% vinyl acetate ..hy n- 60 Chain-stopped linear polyester plasticizer ".40 3PbO-BbSO'4-H2O (stabilizer) 5 The above ingredients were milled together for about 10 minutes on heated difierential rolls until a homogeneous mixture of this material was obtained. Another milled sample was prepared exactly as above using the same formulaterials waspressed into the form ofsolid sheets. various tests with which were then subjected to the following results:

Table ;I

Percent Cold Tem- Plasticized Composition Elonperature gation Flexibility.

Copolymer of vinyl chloride and vinyl acetate, 2, 830 V 385 30? C. Polyvinyl chloride v 2, 680 345" l5 0.

Table II Heat Aging 7 Days at C. Percent 7 Change Plasticizcd Composition Percent in Tensile, Change Elonga- Elonp. s. i. in tion gation Tensile Copolymer of vinyl chloride and vinyl acetate.. 2,-980- +5. 3 380 1.3 Polyvinyl chloride 2, 820 +5. 2 340 -l.4

. Table III IMMERSION IN SAE NO. ZO'OI L 4 HOURS'AT 70 C.

Exposure of each of the aforementioned plasticized compositions to ultraviolet light and in a weatherometer for hours and 350 hours, respectively, showed no effect with regard-to the ultraviolet light on the plasticizedcomposition and only a slight change in color as a result of the weatherometer exposure.

It will, of course, be apparent to those skilled in the art that'other vinyl halide resins as Well as other chain-stopped, liquid linear polyesters, many examples of which have been giiven in our aforementioned-patent application, may be employed in place of the vinyl halide resins and liquid chain-stopped polyesters used'above without departing from the scope of the invention. Thus, we may use other polymers of vinyl halides and copolymers of other vinyl halide comonomers such as, for instance, a copolymer of vinyl chloride and; vinyl propionate, etc. Additional examples of chain-stopped, linear,- liquid polyesters which may be employed are, for instance, the

products of reaction of adipic acid, dipropylene glycol and iso-octyl alcohol; the product of yreact-ion of adipic acidbpropylene glycol and 11-05:- tanol; the product "of reaction of adipic acid,

ae mre octylene glycol and n-octyl alcohol; the product of reaction of adipic acid, propylene glycol and n-decylene alcohol; the product of reaction of adipic acid, propylene glycol and 2'-ethylhexanol; etc.

It will also be apparent to those skilled in the art that other methods of compounding and incorporating the plasticizer may be used as, for instance, spraying the plasticizer into finely divided particles of the vinyl halide resin, etc. The amount of plasticizer used in each case may be varied at will and within wide limits and we do not intend to be limited to any particular range since the properties of the plasticized vinyl halide resin are dependent to a large extent on the amount ofplasticizer incorporated. In many applications we have found it advantageous'to use from to 70 per cent of the plasticizer based on the total weight of the vinyl halide resin and the plasticizer. Preferably, we may use from 25 to 60 per cent of the plasticizer based on the total weight of the latter and the vinyl halide resin.

In addition, other heat stabilizers than the lead oxide used in the foregoing example may also be employed as, for instance, lead silicate, tribasic lead sulfate (3PO.PbSO4.H2O), lead carbonate, lead trimethylsilanolate, etc. The stabilizer is preferably present in an amount equal to from about 0.5 to 10 or per cent, by weight, based on the weight of the vinyl halide resin. Although amounts in excess of 15 per cent may be employed, for economical reasons smaller amounts are preferred. The aforementioned tribasic lead sulfate has unexpectedly imparted greatly improved properties to the plasticized vinyl halide resin as compared to when the stabilizer comprised, for example, litharge.

In the compounding of the plastic compositions for various uses, there may be included materials such as fillers, e. g., lithopone, titanium dioxide, etc. as well as other common plasticizers such as, for example, dioctyl phthalate, tricresyl phosphate, etc., pigments and other modifying materials, without detrimental effect upon the heat, light and electrical stability of the plasticizing materials. For optimum electrical properties, it is highly desirable that the acid value of the chainstopped linear polyester be below 5, for instance, from 0.1 to 2.

The foregoing chain-stopped linear polyesters may be used to plasticize other halogen-containing resinous and rubber-like products, for instance, polyvinylidene products and copolymers thereof (e. g., polyvinylidene chloride and copolymers thereof, neoprene, chlorinated paraffin wax, chlorinated rubber, etc.). These same plasticizers may be used also to plasticize many cellulose esters and ethers, acrylic acid ester polymers, urea and melamine resins, polyvinyl formal and polyvinyl butyral resins, alkyd resins, etc. The claimed plasticized compositions may be mixed with many other synthetic resins and rubbers in varying proportions to modify the properties of the latter in many instances.

' The claimed plasticized compositions can be usedfor making shower curtains, table cloths, raincoats, etc. They are eminently suitable for insulating electrical conductors as, for instance, copper conductors, etc. Copper cores insulated with the claimed plasticized compositions, for instance, with the plasticizer found in Example 1, are extremely heat-stable and exhibit good electrical characteristics, especially when the acid value of the plasticizer is below 2. The accompanying drawing shows an insulated conductor comprising a'metallic core I and an outer insulation 2 comprising a vinyl halide resin plasticized with the liquid compositions disclosed and claimed in our aforementioned copending application.

What I .claim as new and desire to secure by Letters Patent of the United States is:

1. A composition of matter comprising (1) a vinyl halide resin selected from the class consisting of polyvinyl chloride and copolymers of vinyl chloride and vinyl acetate in which the vinyl acetate comprises a minor proportion of the total weight of the vinyl chloride and vinyl acetate; and (2) a plasticizer for (1) comprising an alcohol chain-stopped, liquid, heat-stable, permanently fusible composition comprising the product of reaction under heat of a mixture of ingredients in the following molar ratio and consisting essentially of (a) from 4 to 8 mols of a dicarboxylic acid selected from the class consisting of adipic and azelaic acids, (b) n-1+rc moles of a dihydric alcohol selected from the class consisting of propylene glycol and dipropylene glycol, where n is equal to the number of mols of the dicarboxylic acid and a: is equal to a slight molar excess of the dihydric alcohol necessary to effect complete 'esterification, and (0) about 2 mols of a monohydric linear saturated aliphatic alcohol containing from 6 to 12 carbon atoms, said monohydric alcohol acting as an esterifying chainstopper at each end of, the linear ester chain formed by the reaction of the aforementioned dihydric alcohol and dicarboxylic acid.

2. A composition of matter comprising, by weight, (1) from 40 to 75% polyvinyl chloride and (2) from 25 to 60% of a plasticizer for (1) comprising an alcoholchain-stopped, liquid, heatstable, permanently fusible composition having an acid value below 5 and comprising the product of reaction under heat of a mixture of ingredients in the following molar ratio and consisting essentially of (a) from 4 to 8 mols of adipic acid, (b) n-1+ac mols propylene glycol where n is equal to the number of mols of adipic acid and x is equal to a slight molar excess of the propylene glycol necessary to effect complete esterification, and (c) iso-octyl alcohol, the said iso-octyl alcohol acting as an esterifying chain-stopper at each end of the linear-ester chain formed by the reaction between the aforesaid propylene glycol and adipic acid.

3. A composition of matter comprising, by weight, (1) from 40 to 75% of a vinyl halide resin comprising the conjoint polymerization of a mass containing a predominant proportion of vinyl chloride and a minor proportion of vinyl acetate and (2) from 25 to 60% of a plasticizer for (1) comprising an alcohol chain-stopped, liquid, heatstable, permanently fusible composition having an acid value below 5 and comprising the product of reaction under. heat of a mixture of ingredienm in the" following molar ratio and consisting essentially of (a) from 4 to 8 mols adipic acid, (b) n-1+.1: mols propylene glycol where n is equal to the number of mols of adipic acid and a: is equal to a slight molar excess of the propylene glycol necessary to 'efiect complete esterification, and (c) iso-octyl alcohol, the said iso-octyl alcohol acting as an esterifying chain-stopper at each end. of the linear ester chain formed by the reaction between the aforesaid propylene glycol and adipic acid.

4. A composition of matter comprising (1) a vinyl halide resin selected from the class consisting of polyvinyl chloride and copolymers of vinyl chloride and a vinyl ester of a lower saturated aliphatic monocarboxylic acid in which the vinyl chloride comprises a preponderant proportion of the latter and the vinyl ester, (2) a plasticizer for (l) comprising an alcohol chainstopped, liquid, heat-stable, permanently fusible composition comprising the product of reaction under heat of a mixture of ingredients in the following molar ratio and consisting essentially of (a) from 4 to 8 mols of a saturated aliphatic dicarboxylic acid containing from 4 to 10 total carbon atoms including the carbons in the carboxy groups, (a); n1+x mols of a saturated aliphatic dihydric alcohol containing at least three carbon atoms, where n is equal to the number of mols of the dicarboxylic acid and CL is equal to a slight molar excess of the dihydric alcohol necessary to effect complete esterification, and (0) about 2 mols of a monohydric saturated aliphatic alcohol containing from 6 to 12 carbon atoms, the said monohydric alcohol acting as an esterifying chain-stopper at each end of the linear ester chain formed bythe reaction of the aforementioned dihydric alcoho1 and dicarboxylic acid, and ('3) a stabilizer for (1) comprising a tribasic lead salt corresponding to the formula 5. A composition of matter comprising (1) polyvinyl chloride, (2) a plasticizer for'(1) comprising an alcohol chain-stopped, liquid, heatstable, permanently fusible composition comprising the product of reaction under heat of a mixture of ingredients in the following molar ratio and consisting essentially of (a) from-4' to 8 mols adipic acid, (b)n1+a: mols propylene glycol where n is equal to the number of mols of adipic acid and a: is equal to a slight molar excess of the propylene glycol necessary to effect complete esterification, and (c) an octyl alcohol, the octyl alcohol acting as an esterifying chain-stopper at each end of the linear ester chain formed by the reaction of the aforesaid propylene glycol and adipic acid, and (3) a stabilizer for (1) comprising a tribasic lead salt corresponding to the formula 3PbO.PbSO4.H2O.

6. A composition of matter comprising (1) a viny1 halide resin comprising the resinous product of conjoint polymerization of a mass consisting essentially of a major proportion of vinyl chloride and a minor proportion of vinyl acetate, (2) a plasticizer for (1) comprising an alcohol chainstopped, liquid, heat-stable, permanently fusible composition comprising the product of reaction under heat of a mixtur of ingredients in the following molar ratio and consisting essentially of (a) from 4 to 8 mols adipic acid, (b) n1+.r mols propylene glycol where n is equal to the number of mols of adipic acid and x is equalto a slight molar excess of the propylene glycol necessary to effect complete esterification, and (c) an octyl alcohol, the octyl alcohol acting as an esterifying chain-stopper at each end of the linear ester chain formed by the reaction of the aforesaid propylene glycol and adipic acid, and (3) a stabilizer for (1) comprising a tribasic lead salt corresponding to the formula 3PbO.'PbSO4.H2O.

7. An insulated electrical conductor comprising (1) an electrically conducting metallic core and (2) insulation for said core comprising a vinyl 7 halide resin selected from the class consisting of polyvinyl chloride and a copolymer of .vinyl chloride and vinyl acetate in which the vinyl acetate comprises a minor proportion of the mixture of the total weight of the latter and the vinyl chloride, the said vinyl halide resin containing as a plasticizer therefor an alcohol chainstopped, liquid, heat-stable, permanently fusible composition comprising the product of reaction under heat of a mixture of ingredients in the following molar ratio and consisting essentially of (a) from 4 to 8 mols of a dicarboxylic acid selected from the class consisting of adipic and azelaic acids, (b) n-l-l-x mole of a dihydric alcohol selected from the class consisting of propylene glycol and dipropylene glycol, where n is equal to the number of mols of the dicarboxylic acid and a: is equal to a slight molar excess of the dihydric alcohol necessary to effect complete esterification, and (0) about 2 mols of a linear saturated aliphatic monohydric alcohol containing from 6 to 12 carbon atoms, the said monohydric alcohol acting as an esterifying chain-stopper at each end of the linear ester chain formed by the reaction between the aforesaid dihydric alcohol and dicarboxylic acid.

8. A composition of matter comprising (1) a copolymer of vinyl chloride and vinyl acetate in which the latter ingredient comprises a minor proportion of the total weight of the vinyl chloride and the vinyl acetate; and (2) a plasticizer for (1) comprising an alcohol chainstopped, liquid, heat-stable, permanently fusible composition having an acid number below 5 and a viscosity within the range of from about 250 to 4000 centipoises at 25 C. and comprising the product of reaction under heat of a mixture of ingredients in the following molar ratio and consisting essentially of (a) from 4 to 8 mols adipic acid, (b) nl+a: mols propylene glycol, where n is equal to the number of mols of adipic acid and ac is equal to a slight molar excess of the propylene glycol necessary to effect complete esterification, and (0) about 2 mols iso-octyl alcohol, said iso-octyl alcohol acting as an esterifying chain stopper at each end of the linear ester chain formed by the reaction between the aforesaid propylene glycol and adipic acid.

ROLAND K. GRIFFITH. HENRY C. NELSON, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,020,247 Irey Nov. 5, 1935 2,035,314 Hansley et a1 Mar. 24, 1936 2,035,528 Brubaker Mar. 31, 1936 2,036,009 Wright Mar. 31, 1936 2,075,107 Frazier Mar. '30, 1937 2,141,126 Doolittle Dec. 20, 1938 2,191,056 Wick Feb. 20, 1940 2,407,479 DAlelio Sept. 10, 1946 FOREIGN PATENTS Number Country Date 718,171 Germany Mar. 4, 1942 586,826 Great Britain Apr. 1, 1947 610,138 Great Britain Oct. 12, 1948 

1. A COMPOSITION OF MATTER COMPRISING (1) A VINYL HALIDE RESIN SELECTED FROM THE CLASS CONSISTING OF POLYVINYL CHLORIDE AND COPOLYMERS OF VINYL CHLORIDE AND VINYL ACETATE IN WHICH THE VINYL ACETATE COMPRISES A MINOR PROPORTION OF THE TOTAL WEIGHT OF THE VINYL CHLORIDE AND VINYL ACETATE, AND (2) A PLASTICIZER FOR (1) COMPRISING AN ALCOHOL CHAIN-STOPPED, LIQUID, HEAT-STABLE, PERMANENTLY FUSIBLE COMPOSITION COMPRISING THE PRODUCT OF REACTION UNDER HEAT OF A MIXTURE OF INGREDIENTS IN THE FOLLOWING MOLAR RATIO AND CONSISTING ESSENTIALLY OF (A) FROM 4 TO 8 MOLS OF A DICARBOXYLIC ACID SELECTED FROM THE CLASS CONSISTING OF ADIPIC AND AZELAIC ACIDS, (B) N-1+X MOLES OF A DIHYDRIC ALCOHOL SELECTED FROM THE CLASS CONSISTING OF PROPYLENE GLYCOL AND DIPROPYLENE GLYCOL, WHERE N IS EQUAL TO THE NUMBER OF MOLS OF THE DICARBOXYLIC ACID AND X IS EQUAL TO A SLIGHT MOLAR EXCESS OF THE DIHYDRIC ALCOHOL NECESSARY TO EFFECT COMPLETE ESTERIFICATION, AND (C) ABOUT 2 MOLS OF A MONOHYDRIC LINEAR SATURATED ALIPHATIC ALCOHOL CONTAINING FROM 6 TO 12 CARBON ATOMS, SAID MONOHYDRIC ALCOHOL ACTING AS AN ESTERIFYING CHAINSTOPPER AT EACH END OF THE LINEAR ESTER CHAIN FORMED BY THE REACTION OF THE AFOREMENTIONED DIHYDRIC ALCOHOL AND DICARBOXYLIC ACID. 